Novel photographic products and processes



United States Patent Oilfice Patented Jan. 3, 1967 3,295,973 NOVELPHOTOGRAPHIC PRODUCTS AND PROCESSES Elkan R. Blout, Belmont, Saul G.Cohen, Lexington, and

Milton Green and Myron S. Simon, Newton, Mass., assignors to PolaroidCorporation, Cambridge, Mass., a corporation of Delaware No Drawing.Continuation of application Ser. No. 813,702, May 18, 1959. Thisapplication Nov. 3, 1965, Ser. No. 506,280

6 Claims. (Cl. 96-29) This application is a continuation of ourcopending US. application, Serial No. 813,702, filed May 18, 1959 (nowabandoned), which, in turn, is a continuation-inpart of our copendingUS. application, Serial No. 697,809, filed November 21, 1957 (nowabandoned).

This invention relates to photography and more particularly to productsand processes for the development of photosensitive silver halideelements.

It is a primary object of the present invention to provide noveldiffusion-transfer photographic processes and products whereby improvedcontrol of the transfer of mobile dye developer to an image-receivinglayer may be obtained.

A further object of the present invention is to provide novelphotographic processes and products for obtaining color images by adiffusion-transfer process wherein a dye developer is initially presentin the form of a hydrolyzable dye developer and wherein saidhydrolyzable dye developer is subjected to hydrolysis during processing.

A still further object of the present invention is to provide novelphotographic processes and products wherein a hydrolyzable dye developeris employed and said dye developer is of relatively low mobility untilhydrolysis occurs.

A still further object of the present invention is to providephotographic processes and products for use in monochromatic andmulticolor diffusion-transfer processes utilizing hydrolyzable dyedevelopers, which dye developers contain groups removable duringphotographic processing, to provide thereby improved color rendition.

A still further object of the present invention is to provide novelprocesses for the development of silver halide emulsions, in which thenovel developing agent is capable of developing a latent image andimparting a positive colored image of said latent image to a superposedimagereceiving layer.

A still further object of the present invention is to provide novelphotographic processes and products for obtaining color images bydiffusion-transfer processes which employ hydrolyzable dye developers,which dye developers comprise the hydrolyzable alkoxalyl and aryloxalylesters of specified dye developers.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the several steps and the relationand order of one or more of such steps with respect to each of theothers, and the product possessing the features, properties and therelation of elements which are exemplified in the following detaileddisclosure, and the scope of the application of which will be indicatedin the claims.

For a fuller understanding of the nature and objects of the invention,reference should be had to the following detailed description.

The compounds employed in the present invention possess the propertiesof both a dye and a developing agent; thus they may be referred to asdye developers. The nature of these dye developers will be describedhereinafter.

The photographic processes and compositions disclosed herein areparticularly useful in the treatment of a latent image present in aphotosensitive element, such as an exposed silver halide emulsion,whereby a positive dye image thereof may be imparted to another element,herein referred to as an image-carrying or image-receiving element.

The copending application of Howard G. Rogers, Serial No. 748,421, filedJuly 14, 1958 (now US. Patent No. 2,983,606, issued May 9, 1961), acontinuation-in-part of Serial No. 415,073, filed March 9, 1954 (nowabandoned), discloses diffusion-transfer reversal processes wherein aphotographic negative material such as a photographic element comprisingan exposed silver halide emulsion layer containing a latent image, isprocessed to impart to an image-"receiving element a reversed orpositive dye image of .said latent image by permeating into saidemulsion layer a suitable liquid processing composition and bringingsaid emulsion layer into superposed relationship with an appropriateimage-receiving layer. It is an object of this invention to provideadditional compounds suitable for use in such processes.

In carrying out the process of this invention, a photosensitive elementcontaining a silver halide emulsion is exposed and wetted with a liquidprocessing composition. for example, by immersing, coating, spraying,flowing, etc., in the dark, and the photosensitive element superposed,prior to, during or after wetting, on a sheetlike support element, whichmay be utilized as an image-receiving element. In a preferredembodiment, the photosensitive element contains a layer of hydrolyzab-ledye developer, and the liquid processing composition is applied to thephotosensitive element in a uniform layer as the photosensitive elementis brought into superposed position with an image-receiving element. Itis also within the .scope of this invention to apply the liquidprocessing composition prior to exposure, in accordance with thedisclosure in the copending application of Edwin H. Land, Serial No.498,672, filed April 1, 1955 (now US. Patent No. 3,087,816, issued April30, 1963). The liquid processing composition permeates the emulsion toprovide a solution of dye developer substantially uniformly distributedtherein. As the latent image is developed, the oxidation product of thedye developer is immobilized or precipitated in situ with the developedsilver, thereby providing an imagewise distribution of unoxidized dyedeveloper dissolved in the liquid processing composition. Thisimmobilization is apparently, at least in part, due to a change in thesolubility characteristics of the dye developer upon oxidation, andespecially as regards its solubility in alkaline solutions. It may alsobe due, in part, to a tanning effect on the emulsion by the oxidizeddeveloping agent and to localized exhaustion of alkali due todevelopment. At least part of this imagewise distribution of unoxidizeddye developer is transferred, by imbibition, to a superposedimage-receiving layer or element, said transfer substantially excludingsilver or oxidized dye developer. Under certain circumstances, the layerof the liquid processing composition may be utilized as theimage-receiving layer. The latter element receives a depthwisediffusion, from the emulsion, of unoxidized dye developer Withoutappreciably disturbing the imagewise distribution thereof to provide areversed or positive, colored image of the developed image. Theimage-receiving element may contain agents adapted to mordant orotherwise fix the diffused, unoxidized dye developer. If the color ofthe diffused dye developer is affected by changes in the pH of the imagereceiving element, this pH may be adjusted in accordance with well-knowntechniques to provide a pH affording the desired color. Imbibitionperiods of approximately one minute have been found to give goodresults, but this contact period may be adjusted where necessary tocompensate for variations in tem- 3 perature or other conditions. Thedesired positive image is revealed by stripping the image-receivingelement from the photosensitive element at the end of the imbi bitionperiod.

The compounds of the present invention may be utilized in thephotosensitive element, for example in, on or behind the sliver halideemulsion, or they may be utilized in the image-receiving element. In apreferred embodiment, a coating or layer of the compound is placedbehind the silver halide emulsion, i.e., on the side of the emulsionadapted to be located most distant from the photographed subject whenthe emulsion is exposed and preferably also adapted to be most distantfrom the image-receiving element when in superposed relationshiptherewith. Placing the hydrolyzable dye developer behind the emulsionlayer, as in the preferred embodiment, has the advantage of providingincreased contrast in the positive image, and also minimizes anylight-filtering action by the colored dye developer. In this preferredembodiment, the layer of hydrolyzable dye developer may be applied byusing a coating solution so selected as not to induce hydrolysis duringpreparation of the negative and containing about 0.5 to 8%, by weigh-t,of the dye developer. The liquid processing composition above referredto comprises at least an aqueous solution of an alkaline compound, forexample, diethylamine, sodium hydroxide or sodium carbonate. In someinstances, it may contain an auxiliary or accelerating developing agent.If the liquid processing composition is to be applied to the emulsion bybeing spread thereon, preferably in a relatively thin, uniform layer, itmay also include a viscosity-increasing compound comprising afilm-forming material of the type which, when said composition is spreadand dried, will form a relatively firm and relatively stable film. Apreferred film-forming material is a high molecular weight polymer suchas a polymeric, water-soluble ether inert to an alkali solution, as forexample, a hydroxyethyl cellulose or sodium carboxymethyl cellulose.Other film-forming materials or thickening agents whose ability toincrease viscosity is substantially unaffected when left in solution fora long period of time may also be used.

The copending application of Edwin H. Land and Howard G. Rogers, SerialNo. 669,542, filed July 2, 1957, now abandoned, the subject matter ofwhich has been incorporated in Serial No. 194,359, filed May 14, 1962(now US. Patent No. 3,230,082, issued January 18, 1966), disclosesdiffusion-transfer processes of the previously disclosed type whichemploy hydrolyzable dye developers, These hydrolyzable dye developersare disclosed to be initially less mobile and thus prevent prematuretransfer of dye developers which might give rise to highlight stainand/or incomplete color separation. The present application isprincipally concerned with novel hydrolyzable dye developersparticularly applicable for use in the processes therein disclosed.

The dye developers of the present invention comprise dyes, preferablyazo, anthraquinone, indophenol, indoaniline, and azomethine dyes, mostpreferably azo or anthraquinone dyes, characterized in that they containnot less than one and preferably not more than two groups selected fromthe group consisting of the alkoxalyl and aryloxalyl esters of aliphatichydroxyl groups, said dyes being further characterized in that theycontain not less than one and preferably not more than two groupsselected from the group consisting of orthoand para-dihydroxyphenylgroups.

The preferred novel hydrolyzable dye developers of the present inventioncomprise azo, anthraquinone, indophenol, indoaniline, and azomethine dyedevelopers characterized in that they contain not less than one and notmore than two groups within the formula:

wherein R is an alkylene group, preferably a lower alkyl-. ene groupcomprising from 1 to 5 carbon atoms, for example, ethylene,trimethylene, propylene 0H (-(EHOH2) etc.; R is an alkylene groupcomprising not less than two and not more than four carbon atoms, suchas, for example, ethylene, trimethylene, propylene, etc.; n is 0 or aninteger from 1 to 3, inclusive; and R is an alkyl or aryl group; saiddye being further characterized in that it contains not less than oneand not more than two groups selected from the group consisting ofo-dihydroxyphenyl and p-dihydroxy-phenyl groups.

As illustrations of suitable alkyl groups signified by the term R inFormula A, mention may be made of: ethyl, butyl, hexyl, lauryl, etc. Ingeneral, the alkyl group preferably contains from 1 to 12 carbon atomswhere n is 0 and from 1 to 4 carbon atoms where n is a positive integerfrom 1 to 3, inclusive.

As examples of suitable aryl groups contemplated by R mention may bemade of phenyl and substituted phenyl groups, e.g., tolyl, etc.

The respective o-dihydroxyphenyl and p-dihydroxyphenyl group or groupsmay be linked to the chromopihore-containing component of the dyemolecule by utilization of a divalent radical or a covalent bond. Asexamples of divalent radicals, suitable for use in the practice of thepresent invention, mention may be made of: divalent organic radicalssuch as alkylene radicals, preferably lower alkylene radicals such asethylene, isopropylene, etc.; sulfonamido; sulfamyl; carboxamido;carbamyl; arylene radicals such as phenylene, etc.; aralkylene radicalssuch as phenethyl, etc.; acyl radicals such O -alkylene-i l etc.; anddivalent radicals which contain more hetero and carbon atoms asconstituent components, as for example In a preferred embodiment ofFormula A, R is an ethylene group and the preferred dyes may becharacterized in that they contain a single alkylene linkedunsubstituted p-dihydroxyphenyl group. Such compounds may be representedby the formula:

While the preferred compounds of the present invention have beendescribed above as containing a delimited number of recurring ethergroups, that is 1 to 4 ether groups, it is to be understood thatpolyether groups of greater magnitude may be employed, where desired, inaccordance with the requirements of the operator.

The novel dyes of the present invention may be prepared by reacting adye developer, preferably an azo, anthraquinone, indophenol,indoaniline, or azomethine dye developer, having not less than one andpreferably not more than two aliphatic hydroxyl groups with an alkyland/or an aryl oXalyl halide such as an alkoxalyl or aryloxalyl bromideor chloride, preferably an alkoxalyl or aryloxalyl chloride. Where thedye developer has additional available reactive hydroxyl groups,reaction may occur at such additional groups.

The compounds of Formula A may be prepared by reacting a dye, preferablyan azo, anthraquinone, indophenol, indoaniline, or azomethine dye,characterized in that it contains not less than one and preferably notmore than two aliphatic hydroxyl groups and said dye is furthercharacterized in that it contains not less than one and not more thantwo groups selected from the group consisting of o-dihydroxyphenyl andp-dihydroxyphenyl groups and halogen and alkyl derivatives thereof; witha compound selected from those represented by the formula:

R o(R -o)n iW wherein R R and n have the same significance as noted inFormula A and W is a halogen radical, preferably a chlorine radical;preferably in a reaction medium comprising a suitable anhydrous halogenacid acceptor, e.g., quinoline, pyridine, etc. The reaction ispreferably per formed on a steam bath, but it is within the scope ofthis invention also to employ temperatures that vary from below roomtemperature to above 100 C. The particular conditions employed will varyaccording to the oxalyl halide and the halogen acid acceptor employed.It will be understood that the aforementioned dye may contain additionalunreacted hydroxyl groups as constituent components of an aromaticsystem.

The praparations of numerous of the dye developers preferred for use insynthesizing the hydrolyzable dye developers of the present inventionare set forth in the following copending U.S. applications:

Serial No. 445,171, filed July 22, 1954, in the name of Richard S.Corley, now abandoned;

Serial No. 449,514, filed August 12, 1954, in the names of Elkan R.Blout and Myron S. Simon, now abandoned;

Serial No. 471,542, filed November 26, 1954 in the names of Elkan R.Blout, Saul G. Cohen, Milton Green, Howard G. Rogers, Myron S. Simon,and Robert B. Woodward, now abandoned, the subject matter of which hasbeen incorporated in Serial No. 1,442 and Serial No. 1,443, both filedJanuary 11, 1960, the former in turn abandoned, the subject matter ofwhich has been incorporated in Serial No. 401,714, filed October 5,1964;

Serial No. 473,458, filed December 6, 1954, in the names of Elkan R.Blout, Saul G. Cohen, Milton Green, and Myron S. Simon (now U.S. PatentNo. 3,077,402, issued February 12, 1963);

Serial No. 478,922, filed December 30, 1954, in the names of Elkan R.Blout, Marilyn R. Cohler, Milton Green, Myron S. Simon and Robert B.Woodward, now abandoned, the subject matter of which has been in-vcorporated in Serial No. 824,785 and Serial No. 824,- 786, both filedJuly 3, 1959, in turn now abandoned, the subject matter of which hasbeen incorporated in, respectively, Serial No. 233,461, filed October26, 1962 (now U.S. Patent No. 3,135,606, issued June 2, 1964) and SerialNo. 318,827, filed October 25, 1963 (now U.S. Patent No. 3,209,016,issued September 28, 1965) Serial No. 485,342, filed January 31, 1955,in the name of Richard S. Corley (now U.S. Patent No. 2,983,605, issuedMay 9, 1961) Serial No. 485,840, filed February 3, 1955, in the names ofElkan R. Blout and Howard G. Rogers;

Serial No. 521,874, filed July 13, 1955, in the names of Elkan R. Blout,Milton Green, Myron S. Simon, and Howard G. Rogers, now abandoned, thesubject matter of which has been incorporated in Serial No. 799,427,filed March 16, 1959 (now U.S. Patent No. 3,076,820, issued February 5,1963);

Serial No. 522,848, filed July 18, 1955, in the names of Elkan R. Blout,Sydney Kasman and Myron S. Simon, now abandoned, the subject matter ofwhich has been incorporated in Serial No. 799,425, filed March 16, 1959,in turn abandoned, the subject matter of which has been incorporated inSerial No. 150,661, filed No- Member 7, 1961 (now U.S. Patent No.3,076,808, issued February 5, 1963);

Serial No. 612,045, filed September 25, 1956, in the names of Elkan R.Blout, Milton Green and Howard G. Rog ers, now abandoned, the subjectmatter of which has been incorporated in Serial No. 144,816, filedOctober 18, 1961 (now U.S. Patent No. 3,134,672, issued May 26, 1964);

Serial No. 612,052, filed September 25, 1956, in the names of MiltonGreen and Howard G. Rogers, now abandoned, the subject matter of whichhas been incorporated in Serial No. 165,930, filed January 12, 1962 (nowU.S. Patent No. 3,135,604, issued June 2, 1964);

Serial No. 612,053, filed September 25, 1956, in the name of Myron S.Simon, now abandoned, the subject matter of which has been incorporatedin Serial No. 196,523, filed May 21, 1962 (now U.S. Patent No.3,183,089, issued May 11, 1965), and Serial No. 196,524, filed May 21,1962 (now U.S. Patent No. 3,134,765, issued May 26, 1964);

Serial No. 612,054, filed September 25, 1956, in the names of Helen P.Husek and Myron S. Simon, now abandoned, the subject matter of which hasbeen incorporated in Serial No. 197,259, filed May 24, 1962 (now U.S.Patent No. 3,134,763, issued May 26, 1964), and Serial No. 197,283,filed May 24, 1962 (now U.S. Patent No. 3,236,645, issued February 22,1966);

Serial No. 612,055, filed September 25, 1956, in the name of Helen P.Husek, now abandoned, the subject matter of which has been incorporatedin Serial No. 192,354, filed May 4, 1962 (now U.S. Patent No. 3,134,762,issued May 26, 1964), and Serial No. 192,355, filed May 4, 1962 (nowU.S. Patent No. 3,236,643, issued February 22, 1966);

Serial No. 663,905, filed June 6, 1957, in the names 0 Milton Green andHoward G. Rogers, now abandoned, the subject matter of which has beenincorporated in Serial No. 193,293, filed May 8, 1962 (now U.S. PatentNo. 3,173,906, issued March 16, 1965 and Serial No. 193,326, filed May8, 1962 (now U.S. Patent No.

- 3,222,169, issued December 7, 1965);

Serial No. 669,969, filed July 5, 1957, in the name of Milton Green, nowabandoned;

Serial No. 678,439, filed August 15, 1957, in the name of Myron S.Simon, now abandoned, the subject matter of which has been incorporatedin Serial No. 232,584, filed October 23, 1962 (now U.S. Patent No.3,131,061, issued April 28, 1964), and Serial No. 232,585, filed October23, 1962 (now U.S. Patent No. 3,255,206, issued June 7, 1966);

Serial No. 680,403, filed August 26, 1957, in the name of Milton Green,now abandoned, the subject matter of which has been incorporated inSerial No. 316,498, filed October 16, 1963 now abandoned;

Serial No. 680,434, filed August 26, 1957, in the name of Milton Green,now abandoned, the subject matter of which has been incorporated inSerial No. 230,287, filed October 12, 1962 (now U.S. Patent No. 3,230,086,

7 issued January 18, 1966), and Serial No. 230,288, Serial No. 771,719,filed November 4, 1958, in the names filed October 12, 1962 (now US.Patent No. 3,218,312, of Elkan R. Blout and Richard S. Corley, nowabanissued November 16, 1965); doned, the subject matter of which hasbeen incorpo- Serial No. 680,437, filed August 26, 1957, in the namesrated in Serial No. 193,320, filed May 8, 1962 (now of Elkan R. Bloutand Myron S. Simon (now US. US. Patent No. 3,23 d ebruary 22, 1966);Patent No. 3,047,386, issued July 31, 1962); and Serial No. 680,619,filed August 27, 1957, in the name Serial No. 788,893, filed January 26,1959, in the names of Elkan R. Blout and Myron S. Simon, now abandoned;of Milton Green and Myron S. Simon, now abandoned, Serial No. 685,081,filed September 20, 1957, in the names th u j t ma t r of Which has beenincorporated in 1 of Elkan R. Blout, Milton Green, Howard G. Rogers, 10Serial No. 359,998, filed April 15, 1964.

d Myron S Si b ndoned, the subject mat A preferred compound within thescope of this inventer of which has been incorporated in Serial No.225,- tion comp 656, filed September 10, 1962 (now US. Patent No. (D)3,142,565, issued July 28, 1964), and Serial No. 222,- O O OH 702, filedSeptember 10, 1962 (now US. Patent No. I H 3,208,991, issued September28, 1965); C2H4N=N -L J-NH-OaH4-0-c)- O-O H s rial NO. 703,515, fi1edDecember 18, 1957, in the name LL of Milton Green, now abandoned; H0Serial No. 707,109, filed January 6, 1958, in the names of Elkan R,Blout, Milton Green, Howard G. Rogers 0 0H and Robert B. Woodward, nowabandoned; Serial No. 709,001, filed January 15, 1958, in the names ofMilton Green, Helen P. Husek and Sydney Kasman, now abandoned, thesubject matter of which has been 4--(2',5-dihydroxyphenethyl)-phenylazo] 3 [N incorporated in Serial NO.200,639, filed June 7, 1962 hexoxalyloxyethyl)-carboxamido] 1phenyl-ipyrazo- (now US. Patent No. 3,214,469, issued November 26, 1 Asexamples of further compounds within the scope Serial No. 709,002, filedJanuary 15, 1958, in the names f hi invention mention may b made ofMilton Green and Helen P. Husek, now abandoned, (E the subject matter ofwhich has been incorporated in 3 OH Serial No. 75,128, filed December12, 1960 (now US. Patent No. 3,158,595, issued November 24, 1964);Serial No. 709,005, filed January 15, 1958, in the names of SydneyKasman and Helen P. Husek, now abandoned, the subject matter of whichhas been incorpo- 0 0 rated in Serial No. 75,127, filed December 12,1960, H L & in turn abandoned, the subject matter of which has ih dr hbeen incorporated in Serial No. 339,615, filed January i gg g fl g liggg i phenylazo] 4 ethox 23, 1964; 40 Serial N0. 711,811, filed January29, 1958, in the name a) of Milton Green, now abandoned, the subjectmatter OH 0 0 0 of which has been incorporated in Serial No. 232,613,C2H4N=N -NH-CrHr-0-i J-( J-o-C H filed October 23, 1962 (now us. PatentNO. 3,246,985, 1 LL issued April 19, 1966); HO Serial No. 748,145, filedJuly 14, 1958, in the names of Milton Green and Howard G. Rogers, nowabandoned, OR the subject matter of which has been incorporated inSerial No. 190,804, filed April 27, 1962 (now US. Patent No. 3,186,982,issued June 1, 1965); Serial NO. 755,804, August 18, in the names4-[p-(z',s' dihydroxyphenethyl) phenylazo] 3 [N- of Elkan R. Blout, SaulG. Cohen, Milton Green and (fi-la-uroxalyloxyethyl) carboxamido] 1pheny1-5 y- Serial No. 756,066, filed August 20, 8, in the name 4butoxyethoxyethoxalyloxyethoxy 2 [p (2',5 dihyof Myron S. Simon, nowabandoned; droxyphenethyl)-phenylazo] 1-naphthol 93-[N-butoxyethoxyethoxalyloxyethyl) carbox-amido1-4- [p-(2',5'dihydroxyphenethyl) phenylazo] 1 phenyl-5- pyrazolone OH x4-[5-(2',5-dihydroxyphenyl) u-methyl ethylamino1-1-ethoxalyloxyethylamino-anthraquinone 4-[p-(2,5'-dihydroxyphenethyl)phenylazo] 3 [N- (fl-oct'aoxalyloxyethyl) carboxamido] l-phenyl 5-pyrazolone 4-( 8-ethoxalyloxyethoxy) -1-naphthol.

Example 1 To prep-are 4- [-p- (2,5'-dihydroxyphenethyl-phenylazo]-3-[N-(fl lauroxalyloxyethyl) carboxamido] 1-phenyl-S-pyrazolone, 20 g. of 3-carbethoxy-1-phenyl-5- pyrazolone aredissolved in 200 cc. of ethanolamine and the solution refluxed for 16hours. The excess ethanolamine is then removed in vacuo, the residuedissolved in 100 cc. of ethanol and the resultant solution poured into aliter of dilute hydrochloric acid. The solid product,,3-[N-(B-hydroxyethyl) carboxamido] 1-phenyl-5- pyrazolone, is filtered,crystallized from aqueous ethanol and exhibits a melting point at 160 C.

Analysis for nitr0gen.Calculated: 17.0%. 17.0%.

2,5-bis-acetoxy-phenethyl-aniline, prepared according to the proceduredisclosed in the copendirug U.S. application of Milton Green and HelenP. Husek, Ser. No. 612,063, filed Sept. 25, 1956 (now abandoned andreplaced by Ser. No. 805,673, filed April 1 3, 1959, now US. Patent No.3,019,254, issued Jan. 30, 1962), is diazotized by adding (0.01 mol)thereof to 20 cc. of water, 1.6 cc. of concentrated hydrochloric acid,and treating at approximately 5 C. with 0.7 g. of sodium nitritedissolved in 1 0 cc. of water.

The diazo product is added, dropwise with stirring, to a. solution of(0.01 mol) of 3-[N-(p-hydroxyethyl) Found 10carbox-amido]-1-phenyl-5-pyrazolone in 50 cc. of water, 4.2 g. of sodiumbicarbonate and 10 cc. of ethanol, the solution having previously beencooled to approximately 5 C. The resulting yellow precipitate isfiltered and then treated, under nitrogen, with 25 cc. of ethanol and 25cc. of a 20% sodium hydroxide solution for five minutes at to C.Acidification of the resulting solution with dilute hydrochloric acidand recrystallization from ethanol yields 4-[p-(2,5dihydroxyphenethyl)phenylazo]-S-[N-(B hydroxyethyl) carboxamido] 1- phenyl-S-pyrazolonemelting at 246 to 248 C. The product is soluble in organic solvents suchas acetone and ethanol, resulting in a yellow solution. The absorptionspectrum of this compound in ethanol exhibits a kmax, at 450 my,e=26,300.

1.5 g. of the above yellow dye developer are dissolved in 100 cc. of drypyridine and 2.5 g. of lauroxalyl chloride are added. The solution iswarmed on a steam bath for two hours, taking care to exclude moisture,and then poured into a solution of ice and dilute hydrochloric acid. Thesolid residue which separated is warmed with 50 cc. of absolute ethanol,chilled approximately 12 hours and a small amount of the startingmaterial which had precipitated is removed by filtration. The filtrateis evaporated to dryness, the residue triturated with benzene and thenfiltered. The resultant product is a solid,4-[p-(2,5-dihydroxyphenethyl) phenylazo] 3 [N- (elauroxalyloxyethyl)carboxamido] 1 phenyl-S-pyrazolone.

Analysis for 9.8%.

nitr0gen.Calculated: 9.8%. Found Example 2 To prepare 4-[p-(2,5'-dihydroxyphenethyl)-phenylazo] 3 [N (B hexoxalyloxyethyl)carboxamido]-1 phenyl-S-pyrazolone, 1.5 g. of4-[p-(2,5-dihydr-oxyphenethyl)-phenylazo] 3 [N-(B-hydroxyethyl)-carboxamido]-l-phenyl-5-pyrazolone, prepared according to the proceduredisclosed in Example 1, are dissolved in 100 cc. of anhydrous pyridine,2.5 g. of hexoxalyl chloride are added to the solution and theesterification is conducted under conditions substantially similar tothose disclosed in Example 1. The resultant product is a yellow solid, 4[p (2,5'-dihydroxyphenethyl)-phenylazo]-3-[N-(fihexoxalyloxyethyl)-carboxamido] -1-phenyl-5pyrazolone.

Example 3 To prepare 3 [N (butoxyethoxyethoxalyloxyethyl)- carboxamido]4 [p-(2',5'-dihydroxyphenethyl)-phenylazo]-1-phenyl-5-pyrazolone, 2 g.(0.004 mol) of 4-[p- (2,5-dihydroxyphenethyl) phenylazo] 3 [N(fi-hydroxyethyD-carboxamido] 1 phenyl-S-pyrazolone, prepared accordingto the procedure disclosed in Example 1, are dissolved in 30 cc. ofanhydrous pyridine. 2.1 g. (.006 mol) of butoxyethoxyethoxalyl chlorideare added to the solution, the mixture is warmed in vacuo on a steambath for 3 hours and let stand at room temperature for approximately 12hours. The solution is then mixed with a dilute hydrochloric acidsolution and the resulting granular slurry filtered. The filter cake iswashed with water and dried by concentrating several times, undervacuum, a benzene slurry of the filter cake. The resultant residual gumis washed several times by slurry with benzene and extracted withchloroform. The desired product is obtained by evaporation ofthe'chloroform solution to dryness.

Example 4 jected to alkali hydrolysis. 1.3 g. of the product 2-[p- (2,5dihydroxyphenethyl) phenylazo] 4 hydroxyethoxy-l-naphthol are dissolvedin 30 cc. of anhydrous pyridine and 2.3 g. (.009 mol) ofbut-oxyethoxyethoxalyl chloride are added to the solution. The mixtureis warmed in vacuo on a steam bath for 4 hours and let stand at roomtemperature for approximately 12 hours. The solution is then mixed witha dilute hydrochloric acid solution and the resulting slurry filtered.The filter cake, exhibiting the consistency of a gum, is dried byrepeated concentration from a benzene slurry under vacuum. The resultantresidual oil is washed by slurry with benzene and dissolved in 10 cc. ofchloroform. The chloroform solution is chilled to 40 C. and clarifiedwith Celite. The clarified solution is concentrated to dryness and theresultant gum redissolved in 5 cc. of chloroform. The clarificationprocedure is repeated and the desired product obtained by evaporation ofthe chloroform solution to dryness.

Example 5 To prepare 4- [p-(2',5'-dihydroxyphenethyl)-phenylazo] 3 [N(/8 octaoxalyloxyethyl)-carboxamido]-1- phenyl-S-pyrazolone, 2 g. of4-[p-(2',5'-dihydroxyphenethyl) phenylazo] 3- [N- (,B-hydroxyethyl)-carboxamido] l-phenyl-S-pyrazolone, prepared according to the proceduredisclosed in Example 1, are dissolved in 50 cc. of anhydrous pyridine.2.2 g. of octaoxalyl chloride are added to the solution. The mixture iswarmed in vacuo on a steam bath for 2 hours and let stand at roomtemperature for approximately 12 hours. The solution is then mixed witha dilute hydrochloric acid solution and the resulting slurry filtered.The filter cake is purified by extraction with anacetic-acid/ethyl-acetate mixture. The extract is concentrated todryness and washed several times with a benzene-hexane mixture.

Example 6 A photosensitive element is prepared by coating agelatin-coated film base with a solution containing 5% of 4- [p- 2',5'-dihydroxyphenethyl) -phenylazo] -3- [N-( B- hexoxalyloxyethyl)carboxamido1-l-phenyl-5 -pyrazolone (Formula D as prepared in Example2), in a 4% solution of cellulose acetate hydrogen phthalate in a 50:50mixture, by volume, of acetone and tetrahydrofuran. After this coatinghas dried, a silver iodo-bromide emulsion is applied. Thisphotosensitive element is exposed and processed by spreading an aqueousliquid processing composition comprising:

Percent Sodium carboxymethyl cellulose 4.5 1-phenyl-3-pyrazolidone 0.2Sodium hydroxide 2.5 Potassium bromide 0.2

between said photosensitive element and an imagereceiving element assaid elements are brought into superposed relationship. Theimage-receiving element comprises a cellulose acetate-coated barytapaper which has been coated with a solution comprising N-methoxymethylpolyhexamethylene adipamide in 80% aqueous ethanol. After an imbibitionperiod of approximately 1 minute, the image-receiving element isseparated and contains a yellow positive dye image of the photographedsubject.

Example 7 A photosensitive element is prepared by coating agelatin-coated film base with a solution containing 4% of 4- [p(2',5'-dihydroxyphenethyl) -phenylazo] -3- [N-(B-octaoxalyloxyethyl)carboxamido] 1-phenyl-5-pyrazolone (Formula I as prepared in Example 5),in a 4% solution of cellulose acetate hydrogen phthalate in a 50:50mixture, by volume, of acetone and tetrahydrofuran. After this coatinghas dried, a silver iodobromide emulsion is applied. This photosensitiveelement is exposed and processed by spreading an aqueous liquidprocessing composition comprising:

Percent Sodium carboxymethyl cellulose 4.5 1-phenyl-3-pyrazolidone 0.2Sodium hydroxide 1.5 Potassium bromide 0.2

between said photosensitive element and an image-receiving element assaid elements are brought into superposed relationship. Theimage-receiving element comprises a cellulose acetate-coated barytapaper which 'has been coated with a solution comprising 10%N-methoxymethyl polyhexamethylene adipamide in aqueous ethanol. After animbibition period of approximately 1 minute, the image-receiving elementis separated and contains a yellow positive dye image of thephotographed subject.

Example 8 A photosensitive element is prepared by coating agelatin-coated film base with a solution containing 4% of 4- [p (2',5'dihydroxyphenethyl)-phenylazo]-3-[N-(filauroxalyloxyethyl) carboxamido]l-phenyl-S-pyrazolone (Formula F as prepared in Example 1), in a 4%solution of cellulose acetate hydrogen phthalate in a 50:50 mixture, byvolume, of acetone and tetrahydrofuran. After this coating has dried, asilver iodobromide emulsion is applied. This photosensitive element isexposed and processed by spreading an aqueous liquid processingcomposition comprising:

Percent Sodium carboxymethyl cellulose 5.0 lphenyl-3-pyrazolidone 0.6Sodium hydroxide 3.0 6-nitrobenzimidazole 0.009

between said photosensitive element and an image-receiving element assaid elements are brought into superposed relationship. Theimage-receiving element comprises a cellulose acetate-coated barytapaper which has been coated with a solution comprising 10%N-imethoxymethyl polyhexamethylene adipamide in 80% aqueous ethanol.After an imbibition period of approximately 1 minute, theimage-receiving element is separated and contains a yellow positive dyeimage of the photographed subject.

Example 9 A photosensitive element is prepared by coating agelatin-coated film base with a solution containing 4% of 4-butoxyethoxyethoxalyloxyethoxy 2 [p-(2,5'-dihydroxyphenethyl) phenylazo]l-naphthol (Formula G as prepared in Example 4), in a 4% solution ofcellulose acetate hydrogen phthalate in a 5 0:50 mixture, by volume, ofacetone and tetrahydrofuran. After this coating has dried, a silveriodobromide emulsion is applied. This photosensitive element is exposedand processed by spreading an aqueous liquid processing compositioncomprising:

Percent Sodium carboxymethyl cellulose 5.0 1-phenyl-3-pyrazolidone 0.8Sodium hydroxide 3.0 6-nit-robenzimidazole 0.122,5-bis-ethyleneiminohydroquinone 0.6

1 3 tion of dye developers Whose rate of diffusion might be too rapid topermit effective control if utilized initially in the free or hydrolyzedstate.

Although hydrolysis may initiate immediately, the rate of hydrolysispreferably is less than the rate of development. The rate of hydrolysis,in the preferred embodiment, thus should exhibit a lag behind the rateof development.

In all embodiments of the present invention where the developingfunction is available for reaction prior to hydrolysis, the rate ofhydrolysis, in unexposed areas of the photosensitive element, will behigh in comparison to the rate of hydrolysis in exposed areas due to thefact that hydrolyzable dye developer in the unexposed areas is in areduced form and is thus substantially soluble and hydrolyzable. Inexposed areas of the photosensitive element the dye developer, oxidizedas a result of development, is during the process in a substantiallyinsoluble form and thus a non-hydrolyzable state. The failure of thehydrolyzable dye developer to hydrolyze in exposed areas serves toenhance the immobilization of oxidized dye developer in exposed areas ofthe photosensitive element.

In certain instances, the sensitivity of an associated silver halideemulsion may be affected by a reaction between the associated dyedeveloper and a sensitlzer employed in said silver halide emulsion, orby means of a displacement of sensitizing dye absorbed on the silverhalide, resulting in decreased sensitivity. It has been found that theemployement of the hydrolyzable dye developers of the present inventionas precursors to the ultimately desired dye developers ofiers a means ofrestricting the mobility of the respective dye developers and of thusavoiding or reducing such desensitizing side reactions as mightotherwise occur during storage of the photosensitive product.

It will be noted that the liquid processing composition may, and in theabove examples does, contain at least one auxiliary developer, such asp-methylaminophenol [Metol], 2,4-diaminophenol [Amidol],benzylaminophenol, or a 3-pyrazolidone, such as 1-phenyl-3-pyrazolidone[Phenidone]. The preferred auxiliary developer is 1-phenyl-3-pyrazolidone. This auxiliary developer serves to accelerate andpossibly initiate the action of the dye developer. A portion of the dyedeveloper may be oxidized by an energy transfer reaction with oxidizedauxiliary developer.

The compounds of this-invention may be used also in conventionalphotographic processes, such as tray or tank development of conventionalphotosensitive films, plates or papers containing said compounds toobtain black-and- White, monochromatic or toned prints or negatives. Bythe Way of example, a processing composition suitable for such use maycomprise an aqueous solution of approximately 1% sodium hydroxide, 2%sodium sulfite and 0.05% potassium bromide. After development iscompleted, any unreacted dye developer is washed out of thephotosensitive element, preferably with an alkaline washing medium orother medium in which the unreacted dye developer is soluble. Theexpression toned is used to designate photographic images wherein thesilver is retained with the precipitated dye, Whereas monochromatic isintended to designate dye images free of silver.

It should be noted that the compounds of this invention areself-sufficient to provide the desired color image and do not dependupon coupling reactions to produce the desired color. They thus providea complete departure from conventional photographic color processes inwhich the color is produced by a coupling reaction involving theoxidized developing agent.

It should be noted that it is within the scope of this invention to usemixtures of the compounds to obtain a desired color.

It will be apparent that, by appropriate selection of theimage-receiving element from among suitable known opaque and transparentmaterials, it is possible to obtain either a colored positive reflectionprint or a colored positive transparency. Likewise, the inventiveconcepts herein set forth are adaptable for multicolor work by the useof special photographic materials, for example, film materials of thetype containing two or more photosensitized elements associated with anappropriate number of image-receiving elements and adapted to be treatedwith one or more liquid processing compositions, appropriate dyedeveloper hydrolyzable derivatives suitable to impart the desiredsubtractive colors being incorporated in the photosensitized elements.Examples of such photographic materials are disclosed in US. Patent No.2,647,049 to Edwin H. Land.

The inventive concepts herein set forth are also adaptable for theformation of colored images in accordance with the photographic productsand processes described and claimed in the copending application ofEdwin H. Land, Serial No. 448,441, filed August 9, 1954 (now US. PatentNo. 2,968,554, issued January 17, 1961), and also the copendingapplication of Edwin H. Land and Howard G. Rogers, Serial No. 565,135,filed February 13, 1956.

In the preceding portions of the specification the expression color hasbeen frequently used. This expression is intended to include the use ofa plurality of colors to obtain black, as well as the use of a singleblack dye developer precursor.

Since certain changes may be made in the above products and processesWithout departing from the scope of the invention herein involved, it isintended that all matter contained in the above description shall beinterpreted as illustrative and not in a limiting sense.

What is claimed is:

1. A process of forming transfer images in color which comprises thesteps of exposing a photosensitive element containing a silver halideemulsion and a dye selected from the group consisting of monoazo dyesand anthraquinone dyes containing a single anthraquinonyl nucleus, saiddyes possessing not less than one and not more than two groups withinthe formula:

wherein R is an alkylene group comprising from 1 to 5 carbon atoms; R isan alkylene group consisting of not less than two and not more than fourcarbon atoms; n is selected from the group consisting of 0 and theintegers from 1 to 3, inclusive; and R is selected from the groupconsisting of phenyl groups and alkyl groups, said alkyl groupscomprising from 1 to 12 carbon atoms where n is 0, and from 1 to 4carbon atoms where n is an integer from 1 to 3; said dye furtherpossessing not less than one and not more than two groups selected fromthe group consisting of orthoand para-dihydroxyphenyl groups; effectingremoval of the ester groups by hydrolysis subsequent to photoexposure,developing the latent image contained in the exposed silver halideemulsion, immobilizing the dye in exposed areas of the photosensitiveelement as a function of the point-to-point degree of exposure of saidemulsion, thereby providing an imagewise distribution of dye inunexposed areas of said photosensitive element, and transferring aportion of said imagewise distribution to a superposed irnage-receivinglayer to impart thereto a positive dye image.

2. The process of forming transfer images in color as defined in claim1, wherein said hydrolyzable dye comprises 4- [p-(2',5-dihydroxyphenethyl) -phenylazo] -3- [N- (Bhexoxalyloxyethyl)-carboxamido]-1-phenyl-5-pyrazolone.

3. The process of forming transfer images in color as defined in claim1, wherein said hydrolyzable dye comprises 4- [p-(2',5'-dihydroxyphenethyl) -phenylazo] -3- [N- (5oetaoxalyloxyethyl)-carboxamido]-1-pheny1-5-pyrazclone.

4. The process of forming transfer images in color as defined in claim1, wheren said hydrolyzable dye comprises 4- [p- (2,5'-dihyd-roxyphenethyl) -phenylazo] -3 [N- (Blauroxalyloxyethyl)-carb0xamido]1-phenyl-5-pyrazolone.

5. The process of forming transfer images in color as defined in claim1, wheren said hydrolyzable dye comprises3-[N-(butoxyethoxyethoxalyloxyethyl)-carboxarniphenyl-S-pyrazolone.

6. The process of forming transfer images in color as defined in claim1, wheren said hydrolyzable dye cornl 6 prises 4(butoxyethoxyethoxalyloxyethoxy) -2- [p- (2',5 dihydroxyphenethyl)-phenylazo] -1-naphthol.

References Cited by the Examiner UNITED STATES PATENTS 2,751,295 6/1956Salminen 96-100 2,756,142 7/1956 Yutzy 96-3 2,983,606 5/1961 Rogers 96293,134,672 5/1964 Blout et a1. 96-29 FOREIGN PATENTS 554,935 8/1957Belgium. 569,080 1/ 1959 Belgium.

NORMAN G. TORCHIN, Primary Examiner.

J. TRAVIS BROWN, Examiner.

1. A PROCESS OF FORMING TRANSFER IMAGES IN COLOR WHICH COMPRISES THESTEPS OF EXPOSING A PHOTOSENSITIVE ELEMENT CONTAINING A SILVER HALIDEEMULSION AND A DYE SELECTED FROM THE GROUP CONSISTING OF MONOAZO DYESAND ANTHRAQUINONE DYES CONTAINING A SINGLE ANTHRAQUINONYL NUCLEUS, SAIDDYES POSSESSING NOT LESS THAN ONE AND NOT MORE THAN TWO GROUPS WITHINTHE FORMULA: